Copper complex compounds of substantive azo dyestuffs and a process of making same



Patented Nov. 14, 1950 UNITED STATES PATENT OFFICE COPPER COMPLEXCOMPOUNDS OF SUB- STANTIVE AZO DYESTUFF S AND A PROC- ESS OF MAKING SAMEWalter Wehrli and Ernst Iselin, Basel, Switzerland. assignors to SandozLimited, Basel, Switzerland N Drawing. Application December 11, 1947,Se-

rial No.'791,1'70. In Switzerland December 13,

14 Claims.

SOaH N wherein C=C is a portion of an aryl residue,

shades of outstanding fastness to light, washing I and water and possessa very good power of exhaustion.

The preparation of the azo dyestuffs which are to be transformed intothe copper compounds takes place advantageously. in an alkaline medium,according to the usual methods of coupling, in which either thehydroxynaphthalene sulionic acid or the azine is coupled in the firstinstance with the tetrazotized3.3-dia1koxy-4.4-

diaminodiphenyl.

. As 3.3-dialkoxy-4.4-diaminodipheny1s there come particularly intoconsideration the 3.3'-dimethoxyor 3.3-diethoXy-4.4-diaminodiphenyls.

The addition of pyridine bases has a favourable action both in thecoupling and also in the coppering. 1*

All the sulfonic acids of 1- or Z-hydroxynaphthalene which are capableof coupling are suitable for use as the hydroxynaphthalene sulfonicacids according to the invention, examples being 1 hydroxynaphthalene3.6.8 trisulfonic acid 1-hydroxynaphthalene-3.8-disulfonic acid1-hydroxynaphthalene-3.S-disulfonic acid1-hydroxynaphthalene-4.S-disulfonic acid l-hydroxynaphthalene-3-sulfonicacid 1-hydroxynaphthalene-4-sulfonic acidl-hydroxynaphthalene-5-sulfonic acid 2 hydroxynaphthalene 3.6disulphonic acid 2-hydroxynaphthalene-4-sulfonic acid2-hydroxynaphthalene-6-sulfonic acid Sulfonic acids of dihydroxynaphthalenes such as 1.8-dihydrcxynaphthalene-3.6-disulfonic acid arealso suitabl coupling components.

Suitable azines are for example 2-sulfo-4-hydroxy-afi-naphthophenazine2-sulfo-4-hydroxy-a.p-naphtho-10 methylphenazine 2-sulfo-4-hydroxy (1.18naphtho 10 methoxyphenazine2-sulfo-4-hydroxy-a.p-naphtho-l0-carboxyphene azme5.5-dihydroxy-7.7'-disulfo- 1.1.2'.2 dinaphthazine5.5-dihydroxy-7.7'-disulfo- 1.2.2'.1' dinaphthazine,

the preparation of which is in part described in French patent No.679,164. The azines which can be prepared from1.2-diamino-5-hydroxynaphthalene-'l-sulfonic acid by condensation withortho-diketones such as phenanthrenequinone, also come intoconsideration.

The conversion into the copper complexes can take place according toknown methods which bring about complete or far-reaching splitting offof the alkoxy groups in the radical of the 3.3-dialkoxy-4.4-diaminodiphenyl, as for example heating with an ammoniacalsolution of a copper salt.

The dyestuffs which have not yet been coppered are also suitable fordyeing cotton and regenerated cellulose. The dyeings thus obtained aregreatly improved in their fastness to light by after-treatment withcopper salts on the fibre.

The following examples, without being limitative, illustrate the presentinvention, the parts being by Weight.

Example 1 24.4 parts of dianisidine are tetrazotized as usual andcoupled with ice cooling with 30.4 parts of1-hydroxynaphthalene-4.S-disulfonic acid in the presence of sodiumcarbonate. When the intermediate compound has been formed, an alkalinesolution of the sodium salt from 32.6 parts of the 2-sulfonic acid of4-hydroxy-a.c=naphthophenazine is added. To facilitate the coupling,5-10% by volume of a mixture of pyridine bases can be added. Thedyestuff is isolated after the coupling is finished. It is soluble inwater with a reddish-blue shade and in concentrated suliuric acid with agrey-blue color.

For conversion into the copper'icompound 96.2 parts of the dyestuff aredissolved in 3000 parts of Water and 20 parts of sodium carbonate. 500parts of an ammoniacal copper oxide solution containing parts ofcrystallized copper sulfate and parts of concentrated aqueous ammoniaare added gradually with stirring at 80-90 C. It is stirred for 5 hoursat C. and then boiled under a reflux condenser for 18 hours. The coppercomplex formed is isolated, filtered and dried. It dyes cotton andregenerated cellulose in blue- 3 grey shades of very good fastness tolight and to washing.

For the conversion of the metal-free disazo dyestufi into the coppercomplex compound the above given conditions can be varied within widelimits.

If instead of the 1-hydroxynaphthalene-4.8- disulfonic acid there isused the same quantity of l-hydroxynaphthalene-3.fi-disulfonic acid adyestufi of slightly greener blue-grey shades of excellent fastness tolight is obtained. Similar dyestuffs are obtained by the use ofl-hydroxynaphthalene-3.8-disulfonic acid and2-hydroxynaphthalene-3.6-disulfonic acid.

Example 2 24.4 parts of dianisidine are tetrazotized as usual andcoupled with ice cooling in the presence of sodium carbonate with 38.4parts of lhydroxynaphthalene-3.6.8-trisulfonic acid. After formation ofthe intermediate compound has ensued an alkaline solution of the sodiumsalt from 32.6 parts of the 2-sulfonic acid of 4-hydroxyonB-naphthophenazine is added. It is stirred at 25-30 C. in the presence of 5% byvolume of pyridine until the dyestufi formation is complete. Thedyestuff is then isolated. It dissolves in water with a greenish-blueshade and in concen trated sulfuric acid with a green shade. It dyesregenerated cellulose fibres in greenish-grey-blue shades which byafter-coppering on the fibre undergo hardly any change in shade, buthave their fastness to light very much improved.

For conversion into the copper compound 106.4 parts of the dyestuff aredissolved in 2000 parts of water and 20 parts sodium carbonate. 500parts of ammoniacal copper oxide solution containing 50 partscrystallized copper sulfate and 85 parts of concentrated aqueous ammoniaare added gradually with stirring at about 90 C. It is then boiled andthe boiling continued under a reflux for about hours. The copper complexformed is isolated, filtered and dried.

It dyes cotton and cellulose in bright greenishblue shades of excellentfastness to light and Washing.

In the conversion of the metal-free disazo dyestuff into the coppercomplex compound the conditions given above can be altered within widelimits.

If instead of 32.6 parts of the 2-su1fonic acid of4-hydroxy-afi-naphthophenazine there are used 35.6 parts of the2-sulfonic acid of 4-hydroxyap-naphtho-10-methoxy-phenazine or 37 partsof the 2-sulfonic acid of 4-hydroxy-afi-naphtho- 10-ethoxy-phenazine,there are obtained somewhat brighter dyestuffs of a very similar shade.By the use of 34 parts of the 2-sulfonic acid of 4-hydroXy-ap-naphtho-10methylphenazine or 35.4 parts of the 2-sulfonic acid of 4-hydroxya.3-naphtho-8.11-dimethylphenazine or 3'7 parts of the 2-sulfonic acid of4-hyd1'oxy-a.B-naphthol0-carboxyphenazine similar dyestuffs are obtained.

If in this example 27 parts of 3.3'-diethoxy- 4.4-diaminodiphenyl areused instead of 24.4 parts of dianisidine there is obtained a dyesturfof the same properties.

Example 3 24.4 parts of dianisidine are tetrazotized as usual andcoupled with ice cooling with 32 parts of1.8-dihydroxynaphthalene-3.6-disulfonic acid in the presence of sodiumcarbonate. After the intermediate compound is formed, an alkalinesolution of the sodium salt from 32.6 parts of the 2-sulfonic acid of4-hydroxy-a.B-naphthophenazine is added. It is stirred at 30 C. in thepresence of 10% by volume of pyridine until the formation of thedyestufi is completed. The dyestuif is then isolated. It dissolves inwater With a greenish-blue and in concentrated sulfuric acid with agreenish-grey-blue color.

The same dyestuff is obtained if the tetrazotised dianisidine is firstcoupled with the 2-sulfonic acid of 4-hydroxy-ap-naphthophenazine andthen with the l.8-dihydroXynaphthalene-3.6- disulfonic acid.

For conversion into the copper complex 97.8 parts of the dyestufi aredissolved in 3000 parts of water and 20 parts of sodium carbonate. 500parts of ammoniacal copper oxide solution containing 50 partscrystallised copped sulfate and parts of concentrated aqueous ammoniasolution are added gradually with stirring at C. It is stirred for 5hours at 90 C. and then brought to the boil and boiled for 18 hoursunder a reflux. The copper complex formed is isolated, filtered anddried.

It dyes cotton and cellulose in greenish-bluegrey shades of goodfastness to washing and outstanding fastness to light.

Instead of 32.6 parts of the 2-sulfonic acid of4-hydroxy-a./3naphthophenazine, 38.6 parts of the 2-sulfonic acid of4.10-dihydroxy-afi-naphthophenazine-Q- or -1l-carboxylic acid can beused. This compound is obtained for example from an azo dyestufi of theformula SOSH NH OH by treatment with acids.

Example 4 24.4 parts of dianisidine are tetrazotized as usual andcoupled with ice cooling in the presence of sodium carbonate with 38.4parts of l-hydroxynaphthalene-3.6.8-trisulfonic acid. After formation ofthe intermediate compound has ensued, an alkaline solution of 42.6 partsof the compound of the formula is added. This last- SOzH N namedsubstance can for example be obtained by condensation of1.2-diamino-5-hydroxynaphthalene-l-sulfonic acid withphenanthrenequinone. The product is stirred at l5-20 C. with 7% byvolume of pyridine until the formation of the dyestuff is complete. Thedyestufi is then isolated. It dissolves in water with a greenishblueshade and in concentrated sulfuric acid with a greenish-blue-grey color.

For conversion into the copper complex 116.4

parts of the dyestufi are dissolved in 2500 parts of water and 20 partsof sodium carbonate. 500 parts of an ammoniacal copper oxide solutioncontaining 50 parts of crystallized copper sulfate and 85 parts ofconcentrated aqueous ammonia are added gradually with stirring at 90 C.It is stirred for hours at 90 C., brought to the boil and boiled withstirring under a reflux for about 18 hours. The copper complex formed isseparated, filtered and dried. It dyes cotton and regenerated cellulosein bright greenish-blue shades with outstanding fastness to light and towashing.

Example 5 24.4 parts of dianisidine are tetrazotized as usual andcoupled with ice cooling in the pres ence of sodium carbonate with 38.4parts of 1- hydroxynaphthalene-3.6.8-trlsulfonic acid. After formationof the intermediate compound and alkaline solution of the sodium saltfrom 47L2,parts of the 7.7'-disulfonic acid of 5.5'-dihydroxy-1.1'.2'.2-dinaphthazine is added. It is stirred at 25 C. in the presenceof by volume of pyridine until the formation of the dyestuff iscompleted. The dyestuff is then isolated and if desired purified byreprecipitation. It; dissolves in water with a greenish-blue and inconcentrated sulfuric acid with a blueeg'reen' color.

For conversion into the copper complex 123.2 parts of the dyestufl? aredissolved in 2000 parts of water and 20 parts of sodium carbonate. 500parts of an ammoniacal copper oxide solution containing 50 partscrystallised copper sulfate and 85 parts of concentrated aqueous ammoniaare added gradually with stirring at 8090 C. It is then brought to theboil and boiled with stirring for 20 hours under a reflux. The coppercomplex thus obtained is separated, filtered and dried. It dyes cottonand regenerated cellulose in bright greenish-blue shades of goodfastness to light and to washing. 1,

If instead of 38.4 parts of l-hydroxynaphthalene-3.6.8-trisulfonic acidthere are used 30.4 parts of 1 hydroxynaphthalene 3.6 disulfonic acid,or 30.4 parts of 1-hydroxynaphthalene-3.8- disulfonic acid, or 22.4parts l-hydroxynaphthalene-3-sulfonic acid, or 22.4 partsl-hydroxynaphthalenel-sulfonic acid, dyestuffs of similar shade and verysimilar properties are ob-.

tained.

If in this example instead of the azine named there is used the samequantity of the 7.7-disulfonic acid of5'.,5-dihydroxy-l.2.2.1-dinaphthazine and the process carried out asgiven above, a copper complex'dyeing cotton in bluegrey shades isobtained.

As the azine used in this example contains two places in the. molecule.capable; of coupling, the, .dyestufis. described, are ,capable beforeor,

after conversion into the copper cQmpQ ,ndS,.Q s

being combined with a further molecule of a desired diazo compound.

What we claim is:

1. A copper complex compound of a substantive azo dyestuff of theformula and and R1 and Rzeach represents a member of the a groupconsisting of hydrogen; hydroxy, methyl,

methoxy, ethoxy' and carboxy, the grouping omo can. on

YN=N N=BI sonar wherein Y stands for the residue of a ndro'xyn'aphth'alenesulfonic acid, and" R1" and Rzie'acl'i stands for amember selected from the" group i consisting of hydrogen, hydroxy,methyl, alkoxy wherein Y stands for the residue of a hydroxynaphthalenesulfonic acid.

' 5. A copper complex compound of the substantive azo dyestufi of theformula some H 03.0 OCH: CH-

som some SO|H 6. A copper complex compound of the substantive azodyestufi of the formula on 011.0 OCH: OH

80;N some 808E 7. A copper complex compound of the sub stantive azodyestuff of the formula OH OH 0H,? OCH: 0E

N=N N=N soar son: soa

8. A process for the preparation of a coppercontaining azo dyestuff,which comprises coupling tetra-zotized 3,3-dialk0xy-4,4'-diaminodiphenylwith an equimolecular amount of a hydroxy naphthalene sulfonic acid andwith an equimolecular amount of an azine of the formula wherein R standsfor a, member of the group consistingof and and R1 and R2 eachrepresents a member of the group consisting of hydrogen, hydroxy,methyl, methoxy, ethoxy and carboxy, the grouping pling tetrazotized3,3'-dimethoxy-4,4-diaminodiphenyl with an equimolecular amount of ahydroxynaphthalene sulfonic acid and with an equimolecular amount of anazine of the formula and treating the resultant dyestuff with acopper-yielding agent.

12. A process for the preparation of a coppercontaining azo dyestuif,which comprises coupling 3,3-dimethoxy-4,4-diaminodiphenyl with anequimolecular amount of l-hyclroxy-naphthalene-3,6,8-trisulfonic acidand with an equimolecular amount of the azine of the formula 10 andtreating the resultant dyestuff with a copperyielding agent.

13. A process for the preparation of a coppercontaining azo dyestuff,which comprises coupling 3,3-dimethoxy-4,4-diaminodiphenyl with anequimolecular amount of l-hydroxynaphthalene-3,6-disulfonic acid andwith an equimolecular amount of the azine of the formula and treatingthe resultant dyestufi with a copper-yielding agent.

14. A process for the preparationof a coppercontaining azo dyestuff,which comprises coupling 3,3 -dimethoxy-4,4= diamino diphenyl with anequimolecular amount of 1,8-dihydroxynaphthalene-3,6-disulfonic acid andwith an equimolecular amount of the azine of the formula and treatingthe resultant dyestufi with a copperyielding agent.

WALTER WEHRLI. ERNST ISELIN.

REFERENCES CITED The following references are of record in the file ofthis patent:

UNITED STATES PATENTS Number Name Date 1,786,272 Straub et a1 Dec. 23,1930 1,877,743 Straub et a1. Sept. 13, 1932 2,009,058 Zitscher July 23,1935 2,390,480 West Dec. 4, 1945

1. A COOPER COMPLEX COMPOUND OF A SUBSTANTIVE AZO DYESTUFF OF THEFORMULA